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from water: an overview

Thomas S.Y. Choong


a
, T.G. Chuah
a*
, Y. Robiah
a
, F.L. Gregory Koay
a
, I. Azni
b
a
Department of Chemical and Environmental Engineering,
b
Water Technology Centre, Faculty of Engineering,
Universiti Putra Malaysia, Serdang 43400, Selangor, Malaysia
Tel. +60 (3) 8946 6288; Fax: +60 (3) 8656 7120; email: chuah@eng.upm.edu.my
Received 9 August 2005; Accepted 28 January 2007
Abstract
Arsenic contamination in water, especially groundwater, has been recognized as a major problem of catastrophic
proportions. The toxicology and health hazard also has been reported for many years. Because of the recognition that
arsenic at low concentrations in drinking water causes severe health effects, the technologies of arsenic removal that
have become increasing important. The current regulation of drinking water standard is become more stringent and
requires arsenic content to be reduced to a few parts per billion. There are several treatment methods capable of this
level of performance membranes, coagulation, anion exchange, disposable iron media, softening etc. Treatment
cost, operational complexity of the technology, skill required to operate the technology and disposal of arsenic
bearing treatment residual are factors should be considered before treatment method selection. This paper aims to
review briefly arsenic toxicology and hazards and also the previous and current available technologies that have been
reported in arsenic removal. Residual generation and disposal after treatment will also be discussed.
Keywords: Arsenic; Toxicology; Membrane; Adsorption; Precipitation; GFH; Residual disposal
1. Introduction
Arsenic is a heavy metal with a name derived
from the Greek word arsenikon, meaning potent.
The elements occur in environment in different
oxidation states and form various species, e.g., As
as As(V), As(III), As(0) and As (-III). In oxidized
*Corresponding author.
environment As appears mostly as oxyanions [1].
Arsenic cannot be easily destroyed and can only
be converted into different forms or transformed
into insoluble compounds in combination with
other elements, such as iron. Many impurities
such as lead, iron and selenium may be mixed up
together with arsenic wastes and make it uneco-
nomical to remove.
Arsenic toxicity, health hazards and removal techniques
Desalination 217 (2007) 139166
0011-9164/07/$ See front matter 2007 Published by Elsevier B.V.
doi:10.1016/j.desal.2007.01.015
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 140
Inorganic arsenic generally exists in two pre-
dominant oxidation states, arsenite (NaAsO
2
) and
arsenate (Na
2
HAsO
4
), both of which are toxic to
man and plants. Inorganic arsenic is always
considered a potent human carcinogen, associated
with increased risk for cancer of the skin, lungs,
urinary bladder, liver and kidney [2]. Arsenic
commonly present in water are pH dependant
species of the arsenic (H
3
AsO
4
) and arsenous
(H
3
AsO
3
) acid systems respectively. These anions
have acidic characteristics, and the stability and
dominance of a specific species depend on the pH
of the solution, as shown in Fig. 1. Arsenates are
stable under aerobic or oxidizing conditions,
while arsenites are stable under anaerobic or
mildly reducing conditions.
The presence of arsenic in natural water is
related to the process of leaching from the arsenic
containing source rocks and sediments [4, 5]. It is
generally associated with the geochemical envi-
ronments such as basin-fill deposits of alluvial-
lacustrine origin, volcanic deposits, inputs from
geothermal sources, mining wastes and landfills
[6,7]. Arsenic is a constituent of over 300 mine-
rals and is commonly found in non-ferrous ores
such as copper, lead, zinc, gold and uranium.
Arsenic is a primary constituent of certain ores
(for example the copper mineral enargite) and
occurs as a trace impurity in others [8]. Uncon-
trolled anthropogenic activities such as smelting
of metal ores, use of arsenical pesticides and
wood preservatives agents may also release
arsenic directly to the environment [9].
Presently, arsenic has been used for a variety
of purposes such as treatment of ulcers, tuber-
culosis, syphilis, and many other ailments. More
recently, arsenic has been used as an insecticide,
fungicide, rodenticide, and wood preservative.
The common application of arsenic are in the
manufacture of pesticides (including wood pre-
servatives), dessicants, glass, alloys, electronic
components (semiconductors), pigments, and
pharmaceuticals [10].
Fig. 1. Potential-pH diagram for the arsenic-water system
at unit activity of all species [3].
In this work, the aim of this article is to pro-
vide general description of the toxicity of arsenic,
health hazards, previous and current literatures on
the techniques in treating or removing arsenic.
Different techniques in removing arsenic viz.
adsorption, ion exchangers, membrane, coagu-
lation and precipitation will be discussed. The US
Environmental Protection Agencys (EPA)
Incineration Research Facility has carried out
some tests in evaluating the potential of incinera-
tion as a treatment option for contaminated soils
by arsenic and lead [11]. Due to the volatilization
of arsenic containing compounds emission, the
incineration is not practical for this purpose.
Methods of arsenic wastes residual disposal after
treatment will also be discussed.
2. Toxicity and reported health hazards
Arsenic contamination in natural water is a
worldwide problem and has become an important
issue and challenge for the world engineers,
scientists and even the policy makers. For exam-
ple, chronic arsenic toxicity due to drinking
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 141
arsenic-contaminated water has been one of the
worst environmental health hazards affecting
eight districts of West Bengal since the early
1980s. Detailed clinical examination and inves-
tigation of 248 such patients revealed protean
clinical manifestations of such toxicity. Over and
above hyperpigmentation and keratosis, weak-
ness, anaemia, burning sensation of eyes, solid
swelling of legs, liver fibrosis, chronic lung
disease, gangrene of toes, neuropathy, and skin
cancer are some of the other manifestations [13].
It has also been reported in recent years from
several parts of the world, like USA, China,
Chile, Bangladesh, Taiwan, Mexico, Argentina,
Poland, Canada, Hungary, Japan, and India [4,
1420]
The World Health Organization (WHO)
revised the guideline for arsenic from 0.05 to
0.01 mg/L in 1993 [21]. As the results, Germany
has lowered its permissible limit of arsenic to
0.01 mg L
!1
in 1996 [22], while the Australian
drinking water limits were also lowered from
0.050 to 0.007 mg/l. The French current standard
is 0.015 mg/L, Vietnam and Mexican standard is
0.05 mg/L [23]. In the European Union, the
arsenic standard level is now set to 10 g L
!1
.
The EPA has also eventually implemented the
reduction of permissible values of arsenic in
drinking water from 50 to 10 g/L in light of the
epidemiological evidence to support the carcino-
genic nature of the ingested arsenic and its
connection with liver, lung and kidney diseases
and other dermal effects [http://www.epa.gov/
safewater/arsenic final rule.html, Arsenic in
drinking water rules (66FR 6976, 22 January
2001)]. Many US water utilities protested the
EPA adoption of the WHO recommendation to
revise the arsenic standard of 10 ppb. Naturally
occurring arsenic, adsorbed from rocks through
which water passes, is present in some 4,000 sites
in the US, mainly in the southwest and northeast
states. Utilities supplying water complied with
earlier EPA standards of a 50-ppb maximum
contaminant level (MCL), but the revised com-
pliance levels that reduced this to 10 ppb MCL
represented a big change.
The Malaysia Environmental Quality Act
(1974) has stated that limit of sewage and indus-
trial effluents for arsenic ranged between 0.05
0.1 mg/L. However, an overview of groundwater
contamination in Malaysia has been reported by
Suratman [24]. The Department of Environment,
Malaysia, monitors a programme at areas that are
potentially exposed to contamination that include
industrial, animal burial, rural, urban/suburban,
and agricultural area, golf courses and landfills,
and has found that in general mercury, arsenic,
phenolic compounds and nitrate exceeded bench-
mark values for agricultural, landfill and indus-
trial sites.
Jain and Ali [25] reported comprehensively on
the occurrence and toxicity of arsenic. The toxi-
cology of arsenic is a complex phenomenon and
generally classified into acute and sub-acute
types. The acute arsenic poisoning requiring
prompt medical attention usually occurs through
ingestion of contaminated food or drink. The
major early manifestation due to acute arsenic
poisoning includes burning and dryness of the
mouth and throat, dysphasia, colicky abnormal
pain, projectile vomiting, profuse diarrhea, and
hematuria. The muscular cramps, facial edema
and cardiac abnormalities, shock can develop
rapidly as a result of dehydration [26].
In general, there are four recognized stages of
arsenicosis, or chronic arsenic poisoning [23,27]:
C Preclinical: the patient shows no symptoms,
but arsenic can be detected in urine or body
tissue samples.
C Clinical: various effects can be seen on the
skin at this stage. Darkening of the skin (mela-
nosis) is the most common symptom, often
observed on the palms. Dark spots on the
chest, back, limbs or gums have also been
reported. Oedema (swelling of hands and feet)
is often seen. A more serious symptom is
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 142
keratosis, or hardening of skin into nodules,
often on palms and soles. WHO estimates that
this stage requires 510 years of exposure to
arsenic.
C Complications: clinical symptoms become
more pronounced and internal organ are
affected. Enlargement of liver, kidneys and
spleen have been reported. Some research
indicates that conjunctivitis (pinkeye), bron-
chitis and diabetes may be linked to arsenic
exposure at this stage.
C Malignancy: tumors or cancers (carcinoma)
affect skin or other organs. The affected per-
son may develop gangrene or skin, lung or
bladder cancer.
The results of clinical findings for arsenic
poisoning from drinking arsenic contaminated
water show the presence of almost all the stages
of arsenic clinical manifestation [28]. Diseases
caused by arsenic poisoning are no longer news
but reported worldwide. In Antofagasta, Chile,
over 12% of the population exhibiting dermato-
logical manifestations related to arsenic due to
consumption of high arsenic containing drinking
water [29].Exposure to arsenic via drinking water
(groundwater) has been reported to cause a severe
disease of blood vessels leading to gangrene,
known as blackfoot disease:, in Taiwan [30].
According to some estimates, arsenic in drinking
water will cause 200,000270,000 deaths from
cancer in Bangladesh alone [31]. West Bengal
and India have long known suffered from the
problem of arsenic contaminated groundwater
and claims as the biggest calamity in the world
[1820].
All these cases have provided hints on the
close relationship between the prevalence of
cutaneous lesions and the exposure to drinking
water containing high levels of arsenic. Karim
[32] reported the data of concentration of arsenic
in urine, hair and nails of the affected people in
different arsenic contaminated water ingestion,
including Bangladesh (Table 1). Other minor
Table 1
Concentration of arsenic in urine, hair and nails of the
affected people in different arsenic contaminated water
ingestion episodes [32]
Location Conc. in
urine
(mg/l)
Conc. in
hair
(mg/kg)
Conc.
in nails
(mg/kg)
Fairbanks, AL 0.1783 1.0 4.0
Millard County,
UT
0.025-0.66 0.104.7
Antofagasta,
Chile
0.025-0.77 4.083.4
Lassen County,
CA
0.012.0
Taiwan 0.03660.259
West Bengal,
India
0.032.0 1.81
31.05
1.47
52.03
Bangladesh
a
0.059.42 1.1
19.84
1.3
33.98
a
Average of the few data available in affected areas.
incidents of arsenic poisoning from groundwater,
also have been reported from Minnesota, USA
[33], Millard County, Utah [34,35], Ontario,
Canada [36], Nova Scotia, Canada [37], New
Zealand [38], Nakajo, Japan [39]. Table 2 shows
the distribution of arsenic drinking water concen-
trations from at Millard County, Utah.
3. Treatment and removal of arsenic
3.1. Treatment of arsenic
The relationship between surface-source and
finished water quality, in its simplest form, is that
cleaner source water requires less intense water
treatment and has lower associated acute and
chronic health risks. Common health risks of
drinking water include enteric pathogens, disin-
fection by-products, chemical contamination, and
other toxic compounds. There is little commercial
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 143
Table 2
Distribution of arsenic drinking water concentrations from historical and recent arsenic measurement data for Utah
communities in the study area [35]
Town Number Median Mean Minimum arsenic
conc., ppb
Maximum arsenic
conc., ppb
Standard
deviation
Hinckley 21 166 164.4 80 285 48.1
Deseret 37 160 190.7 30 620 106.6
Abraham 15 116 134.2 5.5 310 67.2
Sugarville 6 92 94.5 79 120 15.3
Oasis 7 71 91.3 34 205 57.8
Sutherland 19 21 33.9 8.2 135 31.8
Delta 46 14 18.1 3.5 125 17.7
interest in investing in plants and technology to
recover arsenic and its compounds when there is
a very limited market for the recovered material
(except in a relative high purity). Safety in hand-
ling and storage has made it even less practical to
recover the arsenic. Dilution and dispersion
methods, however, may attract the interest of
mining and waste disposal operators. The method
provides the possibility for combining numerous
waste streams together and in a way which dilutes
the hazardous contaminants, thus passing any
regulatory limits. It helps in reducing human
exposure to arsenic. This is, in technical practice,
not solving the problem by all mean, but mainly
served as a legislative solution [12].
Conventionally, there are several methods for
arsenic removal. These methods include coagu-
lation and flocculation, precipitation, adsorption
and ion exchange, membrane filtration Alter-
native methods like ozone oxidation, bioremedi-
ation and electrochemical treatments also used in
the removal of arsenic. Each method will be
described briefly together with the related works
in the following sections.
3.2. Coagulation and flocculation
In arsenic removal processes, coagulation and
flocculation are among the most common method
employed. Although the terms coagulation and
flocculation are often used interchangeably or
the single term flocculation is used to describe
both they are, in fact, two distinct processes.
Coagulation is the destabilization of colloids by
neutralizing the forces that keep them apart.
Cationic coagulants provide positive electric
charges to reduce the negative charge (zeta poten-
tial) of the colloids. As a result, the particles
collide to form larger particles. Rapid mixing is
required to disperse the coagulant throughout the
liquid. Flocculation is the action of polymers to
form bridges between the larger mass particles or
flocs and bind the particles into large agglo-
merates or clumps. Bridging occurs when seg-
ments of the polymer chain adsorb on different
particles and help particles aggregate. An anionic
flocculant will react against a positively charged
suspension, adsorbing on the particles and caus-
ing destabilization either by bridging or charge
neutralization.
Aluminium-based coagulation with disinfec-
tion by chlorination is one of the commonly used
treatment methods. McNeill and Edwards [40]
reported a wide range in decreases in soluble
As(V) concentrations for five alum coagulation
treatment plants (674%). Gregor [41] studied the
changing forms and concentrations of arsenic
through aluminium-based coagulation treatment
processes drinking-water treatment plants that
abstract water from the river. His findings
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 144
Fig. 2. (a) SEM micrographs of akaganite particles and (b) SEM micrographs of akaganite particles after As(V) sorption
[89].
provide some insights into the critical steps of
coagulation. For aluminium-based coagulation
with disinfection by chlorination, the form of
arsenic most likely to be present in the treated
water is soluble As(V) because final chlorination
should have converted any remaining As(III) to
As(V). His finding also showed that pre-
chlorination can have an adverse effect on other
water quality parameters such as the formation of
disinfection by-products and the release of taste
and odour compounds from algal cells.
Several feasibility studies have been carried
out using a waste material in the treatment of
arsenical wastewater. Soner Altundoan and
Tmen [42] studied the As(V) removal using
neutralization of liquid phase red muds (LPRM)-
arsenical solution mixtures with acid solution
accompanied with air-agitation and neutralization
of those mixtures with CO
2
gas. They studied the
effect of LPRM/(As(V) solution) volumetric ratio
on the removal of As(V) by co-precipitation
arsenic together with aluminium present as alu-
minate in the LPRM. It is found that As(V) was
removed effectively by LPRM with a volumetric
LPRM/(As(V) solution) ratio of 0.1 from an
arsenical solution in the As(V) concentration of
20 mg dm
!3
. For an efficient removal, it was
found that a Al/As(V) molar ratio of 68 was
required.
Ferric salts are common in the uses of as a
coagulant. Yuan et al. [43] studied a combination
system of ferric sulphate coagulation/sand filtra-
tion in arsenic removal. The method is economic
and effective. Zouboulis and Katsoyiannis [44]
studied arsenic removal by applying a modifi-
cation of a conventional coagulation/flocculation
process. The modifications refer to the intro-
duction of pipe flocculation process in the first
stage of the technique, whereas the second step
has been performed by direct filtration with sand
filters, instead of separation by sedimentation. In
their system, alum or ferric chloride was used as
the coagulant agent enhanced by some organic
polymers. The coagulants were found to be
efficient regarding arsenic removal and had
achieved up to 99% of arsenic removal. Karcher
et al. [45] and Guo et al. [46] also reported the the
uses of ferric chloride and lime-polyferric sulfate
as the coagulants. Han et al. [47] used ferric
chloride and ferric sulphate as flocculants in
arsenic removal. The results have shown a signi-
ficant arsenic removal through adsorption
mechanism onto the ferric complexes present.
Wickramasinghe et al. [48] also studied the
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 145
application of ferric based coagulants in treating
the city groundwater that has been contaminated
by arsenic. The results of the bench-scale experi-
ments conducted indicate that coagulation with
ferric ions followed by filtration is effective in
reducing arsenic concentration in the water tested.
However, the actual efficiency of removal is
highly dependent on the raw water quality.
3.3. Adsorption and ion exchangers
Adsorption is a process that uses solids for
removing substances from either gaseous or
liquid solutions. Adsorption phenomena are ope-
rative in most natural physical, biological, and
chemical systems. Adsorption operations employ-
ing solids such as activated carbon, metal
hydrides and synthetic resins are used widely in
industrial applications for purification of waters
and wastewaters. The process of adsorption
involves separation of a substance from one phase
accompanied by its accumulation or con-
centration at the surface of another. Physical
adsorption is caused mainly by van der Waals
forces and electrostatic forces between adsorbate
molecules and the atoms which compose the
adsorbent surface. Thus adsorbents are charac-
terized first by surface properties such as surface
area and polarity.
For arsenic removal, an ion exchange resin,
usually loaded with chloride ions at the
exchange sites, is placed in vessels. The arsenic
containing water is passed through the vessels
and the arsenic exchanges for the chloride ions.
The water exiting the vessel is lower in arsenic
but higher in chloride than the water entering the
vessel. Eventually, the resin becomes exhaus-
ted; that is, all or most of the exchange sites
that were loaded with chloride ions become
loaded with arsenic or other anions. The chloride
ions that used to be on the resin were exchanged
for the arsenic and other anions that were in the
water being treated.
The effect of the presence of sulfate, com-
petition with other anions, is an important factor
to ion exchanger treatment of arsenic. Sulfate
levers can limit the applicability of ion-exchanger
as arsenic treatment. Jackson and Miller [49]
reported that sulfate was reported not to influence
As(V) sorption by ferrihydrite but resulted in a
considerable decrease in As(III) sorption below
pH 7, with the largest decrease at the lowest pH.
Sorbed As(V) by ettringite [Ca
6
Al
2
(SO
4
)
3
(OH)
12

26H
2
O] was also not desorbable in the presence
of concentrated sulfate and high ionic strength
solutions [50]. On the contrary, sulfate was found
to decrease both As(V) and As(III) sorption on
hydrous ferric oxide in the pH range of 47 [51].
Disagreement in the literatures on the effects of
sulfate on As(V) and As(III) sorption may have
derived from different experimental conditions.
Scattered research has already been conducted
on a wide variety of sorbents. Some of the
reported sorbents include zeolites, goethite, clay,
kaolinites, activated carbon, chitosan beads, coco-
nut husk, coal, fly ash, ferrous iron, alumina,
zirconium oxide, red mud, petroleum residues,
rice husk, human hair, sawdust, manganese
greensand, orange juice residues, akaganite-
nanocrystal and chome waste.
Activated carbon is also commonly used as the
material in arsenic treatment [5254]. Eguez and
Cho [55] measured the adsorption of As (III) and
As (V) using activated carbon at various pH
values. From the effect of temperature on adsorp-
tion, they could determine the isoteric heat of
adsorption. Other researchers [53,56] impreg-
nated carbon with various metal ions such as iron
oxide in order to improve arsenic adsorption. The
iron oxide impregnated activated carbon has
shown higher As(III) and As(V) removals com-
pared with the non-impregnated carbon.
Rajakovic [57] found that carbon pretreated
with Ag
+
or Cu
2+
ions improved As(III) adsorp-
tion but reduced As(V) adsorption. Evdokimov et
al. [58] reported that arsenic adsorption can be
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 146
improved by impregnating carbon with ferric
hydroxide or tartaric acid. Rajakovic and
Mitrovic [59] showed that chemically treated
activated carbon exhibits high adsorption capa-
city for arsenic.
Lorenzen et al. [8] studied the factors (such as
solution pH, carbon type and carbon pretreatment
and elution of the arsenic from loaded carbon)
that affect the mechanism of the adsorption of
arsenic species on activated carbons. They found
that As(V) is more effectively removed from
solution by using activated carbon with high ash
content and pre-treatment of the carbon with
Cu(II) solutions improves its arsenic removal
capacity.
In these studies, commercially available acti-
vated carbons were used. The use of commercial
activated carbon is not suitable for developing
countries because of its high cost. The prepa-
ration of low cost adsorbent for water purification
and wastewater treatment has been reviewed by
Pollard et al. [60] and Bailey et al. [61]: agricul-
tural wastes like rice husk [62,63], coconut husk
[64], amine modified coconut coir [65], car-
bonised wood powder [66], sawdust [67], orange
juice residues [68] and waste tea fungal biomass
[69].
Iron oxides also have been widely used as
sorbents to remove contaminants from waste-
water and liquid hazardous wastes compared to
activated carbon. Removal has been attributed to
ion exchange, specific adsorption to surface
hydroxyl groups or coprecipitation. Hydrous
ferric oxide (HFO) is an important sorbent in
wastewater treatment especially for hazardous
chemical. Olivier et al. [70] removed arsenic
groundwater by filtering the water through sand
and zero-valent iron. As(V) sorbed on the form-
ing hydrous ferric oxides (HFO) resulted from the
oxidation of iron.
Different similar sorbent materials have been
also used, including amorphous iron hydroxide
[71] and ferric hydroxide [7274]. Other types of
ferric products, such as ferrihydrite [75], silica
that containing iron (III) oxide [76], iron-oxide
impregnated activated carbon [77], Ce(IV)-doped
iron oxide [78], iron oxide-coated sand [79],
iron(III)-Poly(hydroxamic acid) complex [80],
ferric chloride [[81], Fe(III)-doped alginate gels
[82], nanocomposite adsorbent based on silica
and iron(III) oxide [83], and iron oxide-coated
polymeric materials [84] are also used in arsenic
treatment.
Arsenic removal technology by adsorption
with a commercial granular ferric hydroxide
(GFH) has been developed in the early 1990s
[73,85]. It can be applied in simple fixed bed
reactors, similar to those for activated alumina or
activated carbon. Simplified operation is a key
benefit of the system, which will operate without
the need for chemical pre-feed or pH correction.
GFH has a high adsorption capacity in natural
waters. The work, carried out by Driehaus et al.
[73], shows that GFH possesses high treatment
capacity of 30,00040,000 bed volumes. Jekel
and Seith [86] compared the methods for the
precipitation/flocculation by iron (III)-chloride
and iron (II)-sulphate as well as adsorption on
GFH in a full scale water treatment plant. Their
findings also show that adsorption on granulated
iron hydroxide has proven to be the method
which will provide greater operational reliability
with least maintenance and monitoring efforts.
Ruhland and Jekel [87] had evaluated three
arsenic treatment techniques: direct filtration with
FeCl
3
, adsorptive filtration with FeSO
4
and
adsorption on granulated ferric hydroxide. The
adsorption on granulated ferric hydroxide is
found to be most preferential process for arsenic
removal on the tested conditions.
Earlier research achieved promising results on
a small scale tests in Germany using a granular
form of ferric hydroxide as an adsorption med-
ium. A follow-up resulted in a cooperation
agreement with German chemical company,
Bayer AG, which developed a totally new granu-
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 147
Fig. 3. Schematic diagram of SORB 33 standard process
[88].
lar ferric oxy hydroxide in partnership with
Severn Trent Water of Fort Washington, Penn-
sylvania, USA. Under this collaboration, SORB
33 and Bayoxide

E33, a combination of adsorp-


tion system and ferric oxy hydroxide medium
specifically designed for arsenic removal are
developed [88]. Fig. 3 shows a schematic diagram
of the SORB 33 standard process. It is claimed by
the developer that arsenic removal can be
adsorbed and removed to a level below the drink-
ing water standard of 10 g/L. With SORB 33,
the only factor which needs monitoring is the
pressure drop of water through the adsorbent bed,
which can be done remotely. However, under
high pH conditions high levels of vanadium,
phosphate and silica can reduce the adsorption of
arsenic, requiring more frequent changing.
Deliyanni et al. [8991] synthesized a novel
adsorbent, akaganite-type -FeO(OH) in the
laboratory by precipitation from aqueous solution
of Fe(III) chloride and ammonium carbonate for
arsenic removal. Advantage of this sorbent,
which found to be nanostructured, was its high
surface area and narrow pore size distribution
[89]. On the other hand, the sorbent retained its
high surface area and crystalline for long and
even after its regeneration. The maximum load
capacity was found to be about 100120 mg
As(V) per g of akaganite, when 0.5 g l
!1
akaga-
nite was used at 298 K, which is higher in com-
parison with other sorbents, like hydrous iron
oxides, ferrihydrite and goethite.
Lenoble et al. [92] used the synthesised iron
(III) phosphate to remove arsenic from water.
Results showed that adsorption capacities were
higher towards As (III), leading to Fe
2+
and
HAsO
4
2!
leaching. The high release of phosphate
and iron will exclude its application in drinking
water plants is the main drawback for this sorbent
to be used in waste water treatment.
Other reported works on the metal oxide based
adsorbents include manganese oxide [9294],
zirconium oxide [9599] and alumina [100105].
Most of these studies are carried out in low con-
centration of arsenic solution or batch experi-
ments. Surtherland and Woolgar [106] compared
the treatment methods on arsenic removal using
adsorption (Alcan enhanced activated alumina),
oxidation and co-precipitation, chemical oxida-
tion and adsorption. They found that all tech-
nologies that remove arsenic from groundwater
will at some time produce arsenic waste either as
a solid or a liquid waste sludge. Tatineni Balaji et
al. [107] evaluated the uses of zirconium (IV)
loaded chelating resin (Zr-LDA) with lysine-
Na,Na diacetic acid functional groups for the
removal of As(V) and As(III). From their finding
in column adsorption, the adsorption of As(V) is
more favorable compared to As(III), due to the
faster kinetics of As(V) compared to As(III).
Similar studies were also carried out by Suzuki et
al. [97].
Zeolites have also attracted ever increasing
interest from academic and industrial laboratories.
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 148
They represent an important group of materials
due to their catalytic, sieve and exchange proper-
ties. Works reported on zeolites used as adsorbent
are aluminium-loaded Shirasu-zeolite [108,109],
clinoptilolite and chabazite zeolites [22,110].
Other reported low cost adsorbents include clay
[111], kaolin [112], goethite [113115], fly ash
[116], red mud [117], humic acid [118], human
hair [119], hematite/feldspar [120] and fungal
biomass [121].
3.4. Membrane filtration
Membrane separation is addressed as a pres-
sure driven process. Pressure driven processes are
commonly divided into four overlapping cate-
gories of increasing selectivity: microfiltration
(MF), ultrafiltration (UF), nanofiltration (NF) and
hyperfiltration or reverse osmosis (RO).MF can
be used to remove bacteria and suspended solids
with pore sizes of 0.1 to micron. UF will remove
colloids, viruses and certain proteins with pore
size of 0.0003 to 0.1 microns. NF relies on
physical rejection based on molecular size and
charge. Pore sizes are in the range of 0.001 to
0.003 microns. RO has a pore size of about
0.0005 microns and can be used for desalination.
High pressures are required to cause water to pass
across the membrane from a concentrated to
dilute solution. In general, driving pressure
increases as selectivity increases. Clearly it is
desirable to achieve the required degree of sepa-
ration (rejection) at the maximum specific flux
(membrane flux/driving pressure). Separation is
accomplished by MF membranes and UF mem-
branes via mechanical sieving, while capillary
flow or solution diffusion is responsible for
separation in NF membranes and RO membranes
[122].
Nanofiltration is considered as one of the
methods that can be used to meet regulations for
lowered arsenic concentrations in drinking water
[123]. Waypa et al. [124] studied the arsenic
removal from synthetic freshwater and from
surface water sources by NF and RO. The results
show that both As(V) and As(III) were effectively
removed from the water by RO and NF mem-
branes (NF70, Dow/Filmtec) over a range of
operational conditions. Both membranes can
achieve rejections of 99%. Removal of As(V) and
As(III) was comparable, with no preferential
rejection of As(V) over As(III). This suggests that
size exclusion governed their separation behav-
iour and not the charge interaction. Urase et al.
[125] studied the pH effect on the rejection
change and explained with the extended Nernst-
Planck equation which showed that electrically
charged membranes generally have a higher
rejection for charged solutes than for non-charged
solutes. Vrijenhoek and Waypa [126] also inves-
tigated the behaviour of the membrane. They also
found that it is consistent with the extended
Nemst-Planck equation model predictions for an
uncharged membrane where size exclusion
controls ion retention. However, separation of
arsenic species was a due to a combination of size
exclusion, preferential passage of more mobile
ions, and charge exclusion. Kouti et al. [127]
showed that the membrane material and the mem-
brane pore size distribution influence the un-
charged organic molecules rejections.
Saita et al. [128] studied the effects of
operating conditions in removal of arsenic from
water by nanofiltration. Their findings show that
arsenic rejection was independent of trans-
membrane pressure, crossflow velocity and
temperature. The co-occurrence of dissolved inor-
ganics does not significantly influence arsenic
rejection.
Seidel et al. [129] used loose (porous) NF
membranes to study the difference in rejection
between As(V) and As(III). The rejection of
As(III) was below 30% and was much lower than
the rejection of As(V). The removal of As(V) was
varied between 60% and 90%. Oh et al. [130]
studied the feasibility of removing the arsenic by
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 149
a low pressure NF that was applied in rural areas
with an electricity supply shortage. The NF is
operated by using just a manually operated
bicycle pump. Sato et al. [131] also investigated
the performance of nanofiltration for arsenic
removal. In their studies, both As(V) and As(III)
removal by NF membranes was not affected by
source water chemical compositions. NF mem-
branes could remove over 95% of pentavalent
arsenic. Furthermore, more than 75% of trivalent
arsenic, which is toxic form of arsenic, could be
removed without any chemical additives. An
overview on the nanofiltration is also discussed
by Bruggen and Vandecasteele [132].
Reverse osmosis (RO) membranes have been
identified as another alternative to remove arsenic
in water. Kang et al. [133] had studied the effect
of pH on removing of arsenic using reverse
osmosis. They found that the removal of arsenic
compound is almost proportional to the removal
efficiency of NaCl. The removal of As(V) is
much higher than As(III) over the pH range 310.
The effect of solution pH on the removal of
arsenic using RO membranes was strongly
affected by the solution pH, especially As(IlI).
Ning [134] had reviewed the removal mechanism
of RO and concluded that arsenic in the com-
monly high oxidation states of (V) is very effec-
tively removed by RO. With further attention to
the removal of the weakly acidic arsenic (III)
species in waters by the operation of RO at
sufficiently high pHs made possible by the newer
antiscalants, practical processes can be developed
with RO to remove all major species of arsenic
from water.
Han et al. [47] had studied the feasibility of
combination of flocculation and microfiltration
for arsenic removal from drinking water. Micro-
filtration of the flocculated water had resulted in
rejection of the floes formed by the membrane
thus leading to low turbidity and arsenic removal
in the filtrate. However, with addition of small
amounts of cationic polymeric flocculant can
greatly increase the permeate flux during
microfiltration.
Shih [135] has illustrated an overview of
arsenic removal on pressure driven membrane
processes. In his work, he explored the para-
meters that may influence the arsenic removal
efficiency by membrane technologies such as
source water parameters, membrane material,
membrane types and membrane processes.
Brandhuber and Amy [136] have also carried out
an intensive study on arsenic removal from
drinking water using several membrane filtration
methods via bench and pilot testing. They
summarized the guidelines of selection for arsenic
removal via membrane treatment as tabulated in
Table 3. A few important findings from their
works are RO membranes or tight NF membranes
appear to be able to sustain high rates of arsenic.
Coagulation, as a pretreatment, can be coupled
with membranes of relatively large pore size to
obtained substantial arsenic removal. However,
greater coagulant doses will be required then
compared to As (V).
Preoxidation of As(III) to As(V) followed by
NF may achieve high rates of arsenic removal. If
arsenic is present in the particulate form, mem-
branes of relatively large pore size may be
effective for arsenic removal.
The drawbacks of using of membrane in
arsenic removal are:
C the systems are more costly than other
treatment methods
C the discharge of the concentrate can be a
problem
C water loss associated with concentrate stream
membrane fouling and flux decline
The membrane technology is very little used
when the objective is to remove only the arsenic,
and when this element is the only one contami-
nant in the raw water. The membranes are
justified when the total dissolved solids due to the
presence of sulphates, nitrates, carbonates etc., is
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 150
Table 3
Treatment option for various arsenic bearing sources water characteristics [136]
Source water Treatment option Possible treatment
Filtration alone
Characteristic RO NF UF MF
a
Preoxidation
b
As speciation
As(III)
As (V)
R
R
PE
R
NR
PE
NR
NR
R
NR
As size distribution
Dissolved
Particulate
R
NR
PE
NR
NR
PE
NR
PE
NR
NR
Co-occurrence
NOM
Inorganic
PE
R
PE
PE
NR
NR
NR
NR
NR
NR
R, recommended; NR, not recommended; PE, possibly effective.
a
Removal of other arsenic forms possible with ferric coagulants.
b
Preoxidation is considered as a pretreatment.
important and require a treatment. In practice, the
in-line coagulation used before a membrane treat-
ment (MF or UF) provides very good perfor-
mances. The coagulant plays the role of adsorbent
and the membrane plays the role of physic
separator [137,138]. Several issues, however, still
remain to be resolved before chemical pre-
treatment like coagulation can be applied opti-
mally in the water treatment membrane field.
These issues include the impact of chemical pre-
treatment on the performance of membrane sys-
tems (i.e., membrane reversible fouling, chemical
cleaning frequency), the compatibility of these
chemicals with membrane materials, the optimum
conditions for chemical pre-treatment, and overall
cost and benefits of chemical pre-treatment to MF
and UF membrane systems [139].
Recent advanced in membrane technology in
arsenic removal including electro-ultrafiltration
(EUF) [140]. EUF is found to possess good
potential in treating arsenic from water. The
traditional 100 kDa UF membrane is unable to
remove As(III) or As(V) from water. After apply-
ing electricity to UF, As(V) rejection increased
dramatically. The removal mechanisms adopted
for As(V) were relied on electrophoretic force
and electrochemical reduction.
3.5. Precipitation processes
Four precipitation processes are useful; alum
coagulation, iron coagulation, lime softening, and
a combination of iron (and manganese) removal
with arsenic.
3.5.1. Alum precipitation
Alum precipitation is able to remove solids
and dissolved metals. For the removal of arsenic,
alum is most effective if an oxidizing agent, such
as chlorine, is added ahead of the flocculator and
clarifier and the pH is reduced to 7 or less. It
would probably be necessary to use a number of
chemicals in order to treat the arsenic in the
drinking water. The arsenic removed from the
water would be contained in the alum sludge
from tile clarifier [123].
3.5.2. Iron precipitation
The most outstanding attributes of this
technology are its simplicity, versatility, selec-
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 151
tivity, and low cost. The operator merely adjusts
pH and iron dose to remove the trace elements of
choice to the desired extent. In this process, an
iron compound, such as a ferric salt (for example,
ferric chloride or ferric sulphate), is added to the
untreated water. The arsenic combines with the
iron to form a precipitate (iron oxyhydroxide in
the form of sludge) that settles out in the clarifier.
Following the clarifier, a filter is employed which
removes iron/arsenic particles not taken out in the
clarifier. The best arsenic removal rates are
obtained at pH of less than 8.5 with or without
chlorine [123]. In practice ferric chloride is more
frequently used rather than ferric sulfate Jones et
al. [141] had studied the removal of arsenic (V)
from sulphuric solution. The found that ferrous
iron provides an effective treatment giving resi-
dual dissolved arsenic concentrations of below
1.0 ppm over a range of compositions along with
99.9% removal. They also noticed that ferric iron
treatment is more effective in conjunction with
mixed lime and magnesium hydroxide.
3.5.3. Lime softening
It is well known that lime softening will
remove substances from water other than hard-
ness (calcium and magnesium ions). Arsenic, too,
can be removed by lime softening. However, the
lime softening technology is justified when a
softened water is required. The produced sludge
does not present any added value, and can limit
the use of this technology. For this case, the
suppliers prefer a treatment in two stages: remo-
val of arsenic following with a lime softening
[138]. The arsenic removal efficiencies of the
lime softening process are significantly affected
by the pH and the presence (or absence) of
chlorine. Chlorine is required to oxidize the
arsenic and acid would probably be necessary to
lower the pH of the treated water to acceptable
drinking water levels. The arsenic removed from
the water will be removed together with the lime
sludge produced by the process.
Several works have been reported for this
method. Field et al. [142] had reported in detail
on arsenic treatment for drinking water by lime
softening. Eberhard et al. [143] had patented the
method using lime participation to remove the
arsenic from a sulphur dioxide-containing solu-
tion resulting from scrubbing the flue gas in the
smelting facility. Huang and Rong [144] also
reported the uses of calcium breach and lime in
the treatment of sewage with high arsenic
content.
3.5.4. Combined with iron (and manganese)
removal
There are a number of processes that are used
to remove iron and/or manganese from water by
oxidizing the iron and/or manganese from their
soluble state (valence of 2+) to a higher valence
to form iron and/or manganese precipitates that
can be filtered from the water. One of the pro-
cesses involves a proprietary media. In one varia-
tion of this process, chlorine is injected into the
raw water containing iron and/or manganese and
allowed to react with the iron and/or manganese
in a reaction vessel for a short time a minute or
two. Following the chlorine reaction vessel, sul-
fur dioxide may also be injected into the water
and allowed to react for a short period of time.
The water is then discharged into one or more
filter vessels which contain the proprietary media.
Sorg [145] has reported the important of the
media selection in arsenic removal in this process.
Differences exist between media that result in
different capabilities. Other factors that impact
arsenic removal capacity using this process are
pH in source water, competitive ligands such as
Si, PO
4
, etc and concentration of As and other
ligands. Sorg and Lytle [146] proposed arsenic
selection guide based on Fe/As in source water
(Fig. 4). The arsenic removal is increased when
iron oxide was added the treatment system
(Fig. 5). Kunzru and Chaudhuri [147] reported
that their findings from batch adsorption/
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 152
Fig. 4. Arsenic selection guide based on iron/arsenic in source water [146].
Fig. 5. Arsenic demonstration program, EPA at Climax, MN [146].
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 153
Table 4
Summary of arsenic precipitation processes [123]
Parameters Alum Iron Lime softening Iron and Manganese
Chemicals Cl
2
Acid
Allum
NaOH
Cl
2
Fe
2
(SO
4
)
3
Cl
2
Lime
Acid
Cl
2
FeCl
3
a
SO
2
a
KMnO
4
a
Polymeric aluminium silicate sulfate (PASS)
a
Organic polymer
pH <6.5 6-8 >10.5 7+
Removal, %
with Cl
2
w/o Cl
2
90
20
90
60
90
80
40-90

Initial arsenic conc., g/L 300 300 400 <100


a
Chemical may/may not be needed depending on water chemistry and process employed.
oxidation kinetic tests in fixed-bed operation,
manganese amended activated alumina (MAA)
would be a more effective medium than activated
alumina (AA) in removing arsenic from ground-
water. In their studies, 84.88% (for AA) and
86.89% (for MAA) of the removed arsenic was
recovered, respective, during regeneration.
Kartinen and Christopher [123] reported that
arsenic reductions of perhaps 50% can be
obtained with this process. The other process in
which iron and/or manganese are frequently
removed from water using manganese green-
sand, also called greensand, which is coated
with manganese dioxide. They reported that
arsenic removal rates of 90% may be obtained
from this process [123]. Table 4 shows a sum-
mary of four main precipitation processes. How-
ever, when permanganate is applied intermittently
to the greensand during backwash, the process
will form a layer of MnO
2
on the filter media that
adsorbs multivalent cations. The adsorbed ions
are then held until permanganate is applied again
during backwash. This adsorbed material is
eliminated may be oxidized to insoluble forms
that remain in layers on the greensand. Given this
mechanism of operation, it is not apparent that
greensand filters will be effective for arsenic
oxidation.
3.5.5. Other precipitation methods
Palfy et al. [148] studied the treatment of
arsenic using H
2
O
2
, calcium oxide, ferric sul-
phate, Portland cement as the precipitation agents
and arsenic waste neutralization. Their findings
suggested that a considerable reserve of arsenic
solubility was achieved by relatively high excess
of additives. From their leachate analysis
approved that lime precipitation in combination
with cement solidification can provide relatively
safe material. The solubility of arsenic was
reduced from original value of 6430 mg/l to
0.823 mg/l in leachate from the produced solidi-
ficate. Combination of lime and ferric compounds
used in the treatment of arsenic via precipitation
are also reported by Shi [149], Tahija and Huang
[150], Meng et al. [81,151] and Wang and
Reardon [152]. Other precipitation agents are also
used such as lanthanum salt [153155], Fentons
reagent [156] and bacterial strains [157].
3.6. Oxidation with ozone
Ozone is a type of chemical oxidation process
used for disinfecting drinking water in municipal
water industry. Since ozone is made of oxygen, it
reverts back to pure oxygen after use. After
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 154
Table 5
Performances and limitations of arsenic oxidants.
Oxidants Performances and Limitations of Arsenic Oxidants
Ozone (O
3
) Ozone may be the most satisfactory for pre-oxidation to convert As (III) to As(V) in water
with the requirement to reduce disinfectant byproducts. Limitations are probably fewer on the
use of ozone as a pre-oxidant for arsenic than when O
3
is used after filtration as a primary
disinfectant. Assimilable Organic Carbon (AOC) formation is ameliorated by
coagulation/filtration treatment downstream, and oxidation of bromide, though still possible,
is much less likely during pre-oxidation because the development of a significant ozone
residual is not necessarily required. Ozone pre-oxidation before nanofiltration could present a
problem if the AOC that is formed has a low molecular weight and passes through the
membrane.
Hydrogen peroxide
(H
2
O
2
)
Hydrogen peroxide oxidation was effective but limited by reactions with calcium hydroxide.
After oxidation, the resulting arsenate waste was effectively stabilized using ferric sulfate.
Chlorine (Cl) Chlorine is a good oxidant for As(III), but application must come early in the treatment train
when disinfectant byproduct precursor concentration is high and there is a danger of
producing large concentrations of disinfectant byproducts.
Permanganate Permanganate may work better than chlorine, however, no sufficient information on the
permanganate demand for arsenic oxidation relative to the demand exerted by other
substances.
disinfecting harmful bacteria and/or pollutants, it
generally leaves behind no by-products. Ozone
when added to water which contains arsenic and
soluble iron, will oxidize both arsenic and iron,
forming sites on the ferric hydroxide for arsenic
to adsorb to. The arsenic bearing iron hydroxide
can then be removed by solid liquid separation
processes.
Frank and Clifford [158] showed that under
ambient conditions, all the As(III) was com-
pletely oxidized with oxygen and chlorine within
61 days. Other researchers had investigated the
oxidation of arsenic in the presence of oxygen
[158160] and applying ozone [160]. However,
information on the rates of arsenic oxidation in
groundwater and the specific rate constants of
these studies are often inconsistent.
Kim and Nriagu [161] studied the rates of
oxidation of naturally occurring arsenic in
groundwater samples in the presence of ozone, air
and pure oxygen gas. Air was used to assess the
effect of reduced partial pressure of oxygen on
the oxidation rate. The half-life for As(III) oxida-
tion by ozone was very short, only 4 min. The
half-life for pure oxygen ranged from 2 days to 5
days, and for air a half-life of 9 days. Their
findings showed that ozone can be used to
remove arsenic from groundwater through oxida-
tion, coprecipitation and adsorption reactions
effectively. A comparison of the relative perfor-
mance between ozone and other oxidants e.g.
hydrogen peroxide and chlorine with respect to
oxidation of As is shown in Table 5.
3.7. Biological remediation and other biological
treatments
Biological treatment has been demonstrated to
be a useful alternative to conventional treatment
systems for the removal of toxic metals from
dilute aqueous solution. However, the biopro-
cesses for treating toxic effluents must compete
with existing methods in terms of efficiency and
economy. To its advantages, the biotechnological
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 155
solution to the problem requires only moderate
capital investment, a low energy input, are
environmentally safe, do not generate waste in
most cases, and are self-sustaining. It is expected
that future biotechnological methods of toxic
waste treatment will play a key role as a displace-
ment for the existing methods.
Jong and Parry [162] treated arsenic and other
acidic metal (Cu, Zn, Ni, Fe, Al and Mg) and
sulfate contaminated waters in a bench-scale
upflow anaerobic packed bed reactor by employ-
ing a mixed population of sulfate-reducing
bacteria. More than 77.5% of the initial concen-
trations of As were removed. Their findings have
agreed well to Simonton et al. [163] work who
reported consistent removal for As and Cr
(>6080%) from solution using SRB (Desulfo-
vibrio desulfuricans) in columns containing silica
sand. It is evident that the action of bacterial
sulfate reduction has enhanced the arsenic remo-
val rate. Steed et al. [164] had also developed a
sulfate-reducing biological process to remove
heavy metals from acid mine drainage.
Katsoyiannis and Zouboulis [165] studied the
removal of As(III) and As(V) during biological
iron oxidation. Their results showed that both
forms of arsenic could be efficiently treated for
the concentration range of concentration 50
200 mg/L. The bacteria has found to catalyze the
oxidation of trivalent arsenic and enhanced the
overall arsenic removal. Other reported works
including Mokashi and Paknikar [166] who
studied the arsenic (III) oxidizing processes using
Microbacterium lacticum in the treatment of arse-
nic contaminated groundwater. Papassiopi et al.
[167] also reported the use of iron reducing
bacteria for the removal of arsenic from con-
taminated soils.
Fungal, non-living biomass P. chrysogenum,
an industrial waste with trade name Mycan, was
studied by Loukidou et al. [121] on the removal
of arsenates. The mechanism used in their study
is via the biosorption and an effective As(V)
removal were obtained in laboratory experiments.
The process was mainly influenced by pH and
also the modification procedures.
3.8. Electrochemical treatment
The electrochemical reduction of inorganic
As(III) and As(V) in aqueous solutions has been
studied preoperatively with the objective of maxi-
mizing the yield of elemental arsenic at the
expense of the highly toxic gas arsine, AsH
3
. The
electrochemical removal of As(III) or As(V) from
wastewaters, however, has received little recent
study.
Twardowski [168] reported a method for
removal of As(III) from mineral acids by electro-
chemical reduction to arsenic, which was depo-
sited on a three-dimensional carbon cathode,
using a divided cell and cathode potentials that
disfavoured over-reduction to arsine. Bejan and
Buunce [169] commented that As(V) was inactive
and could only be removed electrolytically by
prior chemical reduction to As (III) in this sys-
tem. They used a carbon cathode and IrO
2
/Ti
anode to study the electrochemical reduction of
As(III) and As(V) in acidic and basic solutions.
Reduction of As(V) is not efficient, only arsine is
removed. However, efficiency can be improved
by added 5% Pd on alumina as catalyst. The
speciation of trivalent arsenic in aqueous solution
is principally AsO
2
!
at pH >10, HAsO
2
or As
2
O
3
at 0 < pH < 10, and AsO
+
at pH < 0 [170]. The
electrochemical reduction is shown as follows:
Cathode: 2H
+
+ 2e
!
6 H
2
As(III) + 3e
!
6 As(0)
As(0) +3e
!
+ 3H
+
6 AsH
3
Anode: H
2
O!2e
!
6 O
2
+ 2H
+
Bisang et al. [171] also studied the feasibility
of removing the arsenic from acid electro-
chemically. They used Cu, Pb, 316L stainless
steel and graphite as cathodic rotating discs. The
best results were achieved for copper where the
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 156
arsenic deposition takes place in a range of
potentials without hydrogen evolution. Long-term
experiments with a pilot plant electrochemical
reactor with a three-dimensional cathode also
showed that arsenic removal with fractional
conversion per pass of 24% is possible.
3.9. Solar oxidation technique
Solar oxidation in individual units (SORAS)
was explored by Garca et al. [172] as alternative
technology to treat arsenic from the groundwater
(Fig. 6). The process is based on photochemical
oxidation of As(III) followed by precipitation or
filtration of As(V) adsorbed on Fe(III)oxides.
Their findings show that the underlying chemistry
is very complex, and the removal efficiency is
affected by the changes in the chemical matrix, or
by changes in the operative conditions. EAWAG,
Swiss Federal Institute of Aquatic Science and
Technology, has currently developed SORAS in
its laboratory and field tested in the WATSAN
Partnership Project in Bangladesh [173]. How-
ever, more studies are requested before this
technology is feasible in practical uses of arsenic
removal.
Fig. 6. Basic principle of SORAS with illumination,
photochemical formation of the reactive oxidants for the
oxidation of As(III) to As(V) and precipitation of
iron(III)(hydr)oxides with adsorbed As(V) [173].
4. Generation and disposal of arsenic residuals
after treatments
As with other production processes, water
treatment systems will produce a residual. Fre-
quently, it is the disposal of the treatment arsenic
bearing residual and not the treatment technology
itself that is the most difficult issue in practice.
Restrictions have been placed on the discharge of
residuals to water bodies and onto land to prevent
further contamination. This section will focus on
residual generation and disposal of five arsenic
removal systems: anion exchange, activated
alumina absorption, iron/manganese removal,
media adsorption, and membrane processes.
4.1. Anion exchanger
A liquid and solid residual may be generated
from an anion exchange system. The liquid resi-
dual consists of the backwash water, regenerant
solution, and rinse water.These waters constitute
1.5 to 10% of the treated water volume depending
on the feed water quality and type of ion ex-
change unit used [174]. The spent regenerant may
contain high levels of arsenic or have a corrosive
characteristic. Spent resin will be produced when
the resin can no longer be regenerated, or when it
becomes poisoned or contaminated. Spent resin
for disposal may be subject to hazardous waste
regulations depending upon the results of a toxi-
city characteristic leaching procedure (TCLP)
test. Disposal of these solid wastes (spent resin)
are via hazardous waste landfill or return to
vendor. In Malaysia, these wastes will be sent to
Kualiti Alam Sdn Bhd, Bukit Nenas, Negeri
Sembilan (the sole hazardous waste management
centre in Malaysia, www.kualitialam.com.my/)
and disposed using proper monitor landfill.
Liquid effluent will be treated via sanitary sewer
or ponds/lagoon [175].
4.2. Activated alumina (AA)
A liquid and/or solid residual may be pro-
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 157
duced from an AA system depending on the type
of operation. If the system is regenerated, a liquid
waste is produced from the backwash, caustic
regeneration, neutralization, and rinse steps. In
some instances, a sludge may be generated from
the regeneration and neutralization streams
because some alumina dissolves during the
regeneration step and may be precipitated as
aluminum hydroxide [176,177] If an aluminum
based sludge is produced because of lowering the
pH of the liquid residual, this sludge will contain
a high amount of arsenic because of its arsenic
adsorption characteristics. This sludge and the
remaining liquid fraction of the solution will
require disposal. Because both residuals contain
arsenic, their disposal may be subject to disposal
requirements.
When the AA has reached the end of its useful
life, the media itself will also become a solid
residual that must be disposed. Because of its
high arsenic removal capacity, an activated alu-
mina system may be operated on a media throw-
away basis rather than a media regeneration basis.
When operated on a throw-away basis, the
exhausted AA media will be the principal residual
produced. This media has the potential of being
classified as a hazardous waste because of its
high arsenic content. A TCLP test is necessary,
therefore, to determine its classification and
ultimate disposal restrictions. Because the AA
media will filter out particulate material in the
source water, the media bed will occasionally
require backwashing. This backwash water will
likely contain some arsenic attached to either the
particulate material or the very fine AA material
that is removed during backwashing. Conse-
quently, the disposal of the backwash water may
also be subject to the disposal requirements [175].
4.3. Adsorption
In this method, contaminated water is passed
through a bed of the specially developed media,
where arsenic is adsorbed and removed from the
water. Two general types of residuals are poten-
tially generated from media adsorption: spent
media and regeneration solutions. Spent media
will be generated from systems that use the media
on a one-time throw-away basis, or from systems
where the media has become exhausted and can
no longer be regenerated, or is no longer effec-
tive. In some cases, depending on manufacturer
policy, spent media may be sent back to the
vendor for reactivation, recovery, or disposal.
No details were provided for regeneration. It
is generally assumed that the same steps as for
ion exchange will be utilized: backwash, regene-
ration, and rinse. Each of these steps will generate
an aqueous residual which will likely be com-
bined. Some of the new adsorption media have
such large arsenic removal capacities that peri-
odic backwashing (with regeneration) is required
to remove the particulate material that is filtered
out during its treatment operation. This backwash
water will likely contain some arsenic that is
attached to the particulate material or any very
fine adsorption media that is removed by the
backwashing process. The waste stream is a
residual that may be disposed of immediately at
the time of backwashing or it may be held and
disposed with the regeneration waste water.
Depending on the concentration of arsenic in the
influent and other factors, the disposal of the
regeneration waste and the backwash water may
be subject to the disposal requirements [175].
4.4. Iron/manganese removal methods
Iron/manganese removal processes, both the
oxidation/filtration and the potassium perman-
ganate greensand techniques, produce a liquid
residual from the filter backwashing step (Fig. 7).
Occasionally, the filter media or greensand needs
to be replaced and this material also becomes a
residual product that must be disposed. Similar to
the backwash and regenerant solution from the
ion exchange and activated alumina processes,
the filter backwash water will contain arsenic, the
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 158
Fig. 7. Schematic of oxidation-filtration Fe/Mn removal process [175].
Table 6
Residual generation and disposal for the various arsenic treatment methods [175]
Treatment method for arsenic Form of residual Residual generation Disposal
Ion exchange Liquid Regeneration streams
Spent backwash
Spent regenerant
Spent rinse stream
Sanitary sewer
Discharge
Evaporation ponds/lagoon
Solid Spent resins Landfill
Hazardous waste landfill
Return to vendor
Activated alumina Liquid Regeneration streams
Spent backwash
Spent regenerant (caustic)
Spent neutralization (acid)
Spent rinse
Liquid filtrate (when brine
streams are precipitated)
Sanitary sewer
Direct discharge
Evaporation ponds/lagoon
Solid Spent alumina
Sludge (when brine streams
are precipitated)
Landfill
Hazardous waste landfill
Land application
Adsorption Liquid Regeneration streams
Spent backwash
Spent regenerant
Spent rinse stream
Sanitary sewer
Direct discharge
Evaporation ponds/lagoon
Iron and manganese
removal processes
Liquid Filter backwash Direct discharge
Sanitary sewer
Evaporation ponds/lagoons
Solid Sludge (if separated from
backwash water)
Spent media
Sanitary sewer
Land application
Landfill
Landfill
Hazardous waste landfill
Membrane processes Liquid Brine (reject and backwash
streams)
Direct discharge
Sanitary sewer
Deep well injection
Evaporation ponds/lagoon
T.S.Y. Choong et al. / Desalination 217 (2007) 139166 159
concentration dependent upon the amount of
arsenic removed and the quantity of backwash
water. Although the liquid fraction of the back-
wash water will contain some soluble arsenic,
most of the arsenic will be associated with the
iron/manganese solids. Depending upon their
arsenic concentration, the disposal of the back-
wash water residual and the spent solid media
residual may be subject to the disposal require-
ments [175].
4.5. Membrane processes
All membrane processes produce a reject
waste product containing the materials, including
arsenic, rejected by the membrane. The reject
water is generally high in total dissolved solids
[174]. Depending on the concentration of the
arsenic and other contaminants in the reject
water, the disposal of this waste may be subject to
the disposal requirements.
Each treatment technology in arsenic removal
described above differs in residual production and
residual management options. Table 6 presents a
summary of these five unit processes, the type of
residual produced, and a list of possible disposal
methods for the residuals.
5. Conclusion
To remove arsenic from wastewaters, the most
commonly used technologies are adsorption onto
activated alumina, and precipitation or adsorption
by metals oxides, predominantly Fe(III) and
membranes. These technologies for removal of
arsenic from wastewaters are most suited to deal-
ing with relatively low concentrations of arsenic,
i.e. the low g/l level. However, the technique of
precipitation, generally using Fe (III) or lime
softening is suited to higher concentrations,
normally at the low mg/l levels. Adsorption is a
method that has been an important method used
in arsenic removal. Most studies are focused on
the type of adsorbent mediums and the economics
of their regeneration. Membrane technology,
especially nanofiltration, becomes a promising
method in arsenic removal and is also widely
considered as the methods that can be used to
meet regulations for lowered arsenic concen-
trations in drinking water. Other alternative
methods also studied for their feasibility in
replacing the current available methods. Future
needs on arsenic removal technology should take
into considerations of reducing the treatment cost,
simplifying the operational complexity of the
technology and disposal of arsenic bearing
treatment residual.
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